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<p>Praseodymium in the +5 oxidation state is a long-sought connection between lanthanide, early-transition and actinide metal redox chemistries. Unique among the lanthanide series, evidence for molecular pentavalent praseodymium species has been observed in the gas phase and noble gas matrix isolation conditions. Here we report the low-temperature synthesis and characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr<sup>5+</sup>(NP<sup><i>t</i></sup>Bu<sub>3</sub>)<sub>4</sub>][X<sup>−</sup>] (where <sup><i>t</i></sup>Bu = <i>tert</i>-butyl and X<sup>−</sup> = tetrakis(pentafluorophenyl)borate or hexafluorophosphate). Single-crystal X-ray diffraction, solution-state spectroscopic, solution magnetometric, density functional theory and multireference wavefunction-based methods indicate a highly multiconfigurational singlet ground state. An inverted ligand field drives this unique electronic structure, which establishes a critical link in understanding the bonding of high-valent metal complexes across the periodic table.</p><p></p>

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Praseodymium in the formal +5 oxidation state

  • 期刊论文

  • 发表日期：

    2025年4月7日

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  • Andrew C. Boggiano,
  • Chad M. Studvick,
  • Sabyasachi Roy Chowdhury,
  • Julie E. Niklas,
  • Haruko Tateyama,
  • Hongwei Wu,
  • Johannes E. Leisen,
  • Florian Kleemiss,
  • Bess Vlaisavljevich,
  • Ivan A. Popov,
  • Henry S. La Pierre

摘要

Praseodymium in the +5 oxidation state is a long-sought connection between lanthanide, early-transition and actinide metal redox chemistries. Unique among the lanthanide series, evidence for molecular pentavalent praseodymium species has been observed in the gas phase and noble gas matrix isolation conditions. Here we report the low-temperature synthesis and characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr5+(NPtBu3)4][X−] (where tBu = tert-butyl and X− = tetrakis(pentafluorophenyl)borate or hexafluorophosphate). Single-crystal X-ray diffraction, solution-state spectroscopic, solution magnetometric, density functional theory and multireference wavefunction-based methods indicate a highly multiconfigurational singlet ground state. An inverted ligand field drives this unique electronic structure, which establishes a critical link in understanding the bonding of high-valent metal complexes across the periodic table.